In 1953, White married Patricia Finegan, whom he met while at West Point.[6] The Whites would have two children, Edward White III (born September 16, 1953) and Bonnie Lynn White (born May 15, 1956). White was a devout Methodist.[9]

White was one of nine men chosen as part of the second group of astronauts in 1962. Within an already elite group, White was considered to be a high-flier by the management of NASA. He was chosen as Pilot of Gemini 4, with Command Pilot James McDivitt. White became the first American to make a walk in space, on June 3, 1965. He found the experience so exhilarating that he was reluctant to terminate the EVA at the allotted time, and had to be ordered back into the spacecraft. While he was outside, a spare thermal glove floated away through the open hatch of the spacecraft, becoming an early piece of space debris in low Earth orbit, until it burned up upon re-entry into the Earth's atmosphere. There was a mechanical problem with the hatch mechanism, which made it difficult to open and to relatch, which added to the time constraint of the spacewalk, and could have threatened the lives of both men if McDivitt had been unable to get the hatch latched, as they could not re-enter the atmosphere with an unsealed hatch.

I'm coming back in... and it's the saddest moment of my life.

— Astronaut Edward H. White while reentering the spacecraft after his EVA, [10]

White's next assignment after Gemini 4 was as the backup for Gemini 7 Command Pilot Frank Borman. He was also named the astronaut specialist for the flight control systems of the Apollo Command/Service Module. By the usual procedure of crew rotation in the Gemini program, White would have been in line for a second flight as the command pilot of Gemini 10 in July 1966, which would have made him the first of his group to fly twice.

In March 1966 he was selected as senior pilot (second seat) for the first manned Apollo flight, designated AS-204, along with Command Pilot Virgil "Gus" Grissom, who had flown in space on the Mercury 4 Liberty Bell 7 mission and as commander of the Gemini 3 Molly Brown mission, and Pilot Roger Chaffee, who had yet to fly into space. The mission, which the men named Apollo 1 in June, was originally planned for late 1966 (perhaps concurrent with the last Gemini mission), but delays in the spacecraft development pushed the launch into 1967.

Charred remains of the Apollo 1 Command Module, in which White was killed along with Gus Grissom and Roger Chaffee

The launch of Apollo 1 was planned for February 21, 1967. The crew entered the spacecraft on January 27, mounted atop its Saturn IB booster on Launch Pad 34 at Cape Kennedy, for a "plugs-out" test of the spacecraft, which included a rehearsal of the launch countdown procedure. Midway through the test, a fire broke out in the pure oxygen-filled cabin, killing all three men.

White's job was to open the hatch cover in an emergency, which he apparently tried to do; his body was found in his center seat, with his arms reaching over his head toward the hatch. Removing the cover to open the hatch was impossible, because the plug door design required venting normally slightly greater-than-atmospheric pressure and pulling the cover into the cabin. Grissom was unable to reach the cabin vent control to his left, where the fire's source was located. The intense heat raised the cabin pressure even more, to the point where the cabin walls ruptured. The astronauts were killed by asphyxiation and smoke inhalation.

The fire's ignition source was determined to be a spark that jumped from a wire on the far left of the spacecraft, under Grissom's seat,[11] but their deaths were attributed to a wide range of lethal hazards in the early Apollo Command Module design and workmanship and conditions of the test, including the highly pressurized 100% oxygen pre-launch atmosphere, many wiring and plumbing flaws, flammable materials used in the cockpit and the astronauts' flight suits, and a hatch which could not be quickly opened in an emergency.[12] After the incident, these problems were fixed, and the Apollo program carried on successfully to reach its objective of landing men on the Moon.

McDivitt-White Plaza is located outside West Hall at the University of Michigan. West Hall formerly housed the College of Engineering and counts James McDivitt and Ed White among its alumni (McDivitt earned his B.S. and White earned his M.S. at the University of Michigan).[37]

The dismantled Launch Pad 34 at Cape Canaveral bears two memorial plaques. One reads, "They gave their lives in service to their country in the ongoing exploration of humankind's final frontier. Remember them not for how they died but for those ideals for which they lived." and the other "In memory of those who made the ultimate sacrifice so others could reach for the stars. Ad astra per aspera, (a rough road leads to the stars). God speed to the crew of Apollo 1."[6]

Eight months after his death, in September 1967, a postage stamp was issued by the United States Post Office, commemorating White's spacewalk, the first-ever by an American.[42] It was the first time in USPO history that the design was actually spread over two stamps (one which featured White, the other his Gemini capsule, the two connected by a tether), which was considered befitting the "twins" aspect of the Gemini mission.[30]

The Omega Speedmaster wristwatch reference 105.003 has come to be known as the "Ed White" as this reference was worn by White during his spacewalk. The Speedmaster remains the only watch qualified by NASA for EVA use.

^Prior to the first graduating class from the U.S. Air Force Academy in 1959, a certain percentage of officers in the U.S. Air Force were drawn from West Point and from the U.S. Naval Academy at Annapolis, Maryland. In any case, the vast majority of officers in the U.S. Armed Forces are educated and trained at the three kinds of R.O.T.C. programs at hundreds of other institutes and universities across the country.

^Kluger, Jeffrey, Apollo 8: The Thrilling Story of the First Mission to the Moon (Henry Holt & Co., 2017), p. 94. "At precisely 6:31 p.m., a spark jumped from a wire on the far left of the spacecraft, beneath Gus Grissom's seat. The wire ran beneath a little storage compartment with a metal door that had been opened and closed many times without anybody noticing that each time the door moved, it abraded a little more of the wire's insulation, finally leaving the wire free to spark at will. When the wire sparked during the plugs-out test, it ignited a small fire that stayed small for only a second or two. Accelerated by the pure oxygen, the flames climbed along the left-hand wall of the spacecraft, feeding on fabric and netting used for storage. That was the worst possible place for a fire to erupt, since it presented Grissom from reaching a latch that would have opened a valve and vented the high-pressure atmosphere, thus slowing the flames."

^"Ed White Elementary School". Clear Creek ISD. Archived from the original on August 11, 2009. Retrieved July 20, 2009. Our school opened in 1965 as El Lago Elementary. The name was changed in 1967 to Edward H. White II Elementary in honor of the life and accomplishments of Edward Higgins White II -- the first American to walk in space.